US10100231B2 - Adhesive having structural integrity and insulative properties - Google Patents

Adhesive having structural integrity and insulative properties Download PDF

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Publication number
US10100231B2
US10100231B2 US15/475,685 US201715475685A US10100231B2 US 10100231 B2 US10100231 B2 US 10100231B2 US 201715475685 A US201715475685 A US 201715475685A US 10100231 B2 US10100231 B2 US 10100231B2
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United States
Prior art keywords
adhesive
article
microspheres
substrate
adhesive composition
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US15/475,685
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US20170204303A1 (en
Inventor
Tianjian Huang
Robert Sandilla
Daniel Waski
Kristina Thompson
John Meccia
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Henkel AG and Co KGaA
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Henkel IP and Holding GmbH
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Priority claimed from PCT/US2011/050965 external-priority patent/WO2012033998A2/en
Priority claimed from US13/826,451 external-priority patent/US9657200B2/en
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Priority to US15/475,685 priority Critical patent/US10100231B2/en
Publication of US20170204303A1 publication Critical patent/US20170204303A1/en
Assigned to Henkel IP & Holding GmbH reassignment Henkel IP & Holding GmbH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HENKEL CORPORATION
Assigned to HENKEL CORPORATION reassignment HENKEL CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SANDILLA, ROBERT, MECCIA, John, THOMPSON, Kristina, HUANG, TIANJIAN, WASKI, DANIEL
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Assigned to HENKEL AG & CO. KGAA reassignment HENKEL AG & CO. KGAA ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: Henkel IP & Holding GmbH
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a non-planar shape
    • B32B1/02—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/28—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer comprising a deformed thin sheet, i.e. the layer having its entire thickness deformed out of the plane, e.g. corrugated, crumpled
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
    • B65D81/38—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents with thermal insulation
    • B65D81/3848—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents with thermal insulation semi-rigid container folded up from one or more blanks
    • B65D81/3858—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents with thermal insulation semi-rigid container folded up from one or more blanks formed of different materials, e.g. laminated or foam filling between walls
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
    • B65D81/38—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents with thermal insulation
    • B65D81/3865—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents with thermal insulation drinking cups or like containers
    • B65D81/3874—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents with thermal insulation drinking cups or like containers formed of different materials, e.g. laminated or foam filling between walls
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J131/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Adhesives based on derivatives of such polymers
    • C09J131/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C09J131/04—Homopolymers or copolymers of vinyl acetate
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/14—Secondary fibres
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/24—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/54—Starch
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/50—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by form
    • D21H21/52—Additives of definite length or shape
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/50—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by form
    • D21H21/52—Additives of definite length or shape
    • D21H21/54—Additives of definite length or shape being spherical, e.g. microcapsules, beads
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/10—Packing paper
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/30—Multi-ply
    • D21H27/32—Multi-ply with materials applied between the sheets
    • D21H27/34—Continuous materials, e.g. filaments, sheets, nets
    • D21H27/36—Films made from synthetic macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/02—Starch; Degradation products thereof, e.g. dextrin
    • C09J2205/11—
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/412—Additional features of adhesives in the form of films or foils characterized by the presence of essential components presence of microspheres
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2403/00—Presence of starch
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2429/00—Presence of polyvinyl alcohol
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2431/00—Presence of polyvinyl acetate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/1376—Foam or porous material containing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24628—Nonplanar uniform thickness material
    • Y10T428/24669—Aligned or parallel nonplanarities
    • Y10T428/24694—Parallel corrugations
    • Y10T428/24711—Plural corrugated components
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249971—Preformed hollow element-containing
    • Y10T428/249972—Resin or rubber element

Definitions

  • the present invention relates to an adhesive composition having improved insulative properties while maintaining structural integrity when applied onto a package.
  • the invention includes an adhesive composition and method of making an adhesive composition in providing insulation to multilayer substrates.
  • Multilayer substrate articles comprise individual substrates bonded together with adhesives.
  • cellulosic sheet e.g., paperboard, cardboard, paper, coated paper, films
  • waterborne adhesives to form containers for consumer products such as cups, food containers, cases, cartons, bags, boxes, envelopes, wraps, lids, clamshells, and the like.
  • Other non-multilayer substrate articles provide sufficient insulation but they are plastic based, e.g., polyurethanes, polystyrenes, and are considered as environmentally unsound,
  • Adhesive Level Effect on Corrugated Board Strength - Experiment and FE Modeling teaches to increase the amount of adhesives interposed between the substrates. However, increasing the amount of the adhesive in the article lengthens the drying time and thereby decreases manufacturing speed. Long drying time or heaters must be used to drive the water out of the substrates, which increases energy consumption.
  • the present invention seeks to improve insulating substrates, through the use of an adhesive composition that adds insulative properties to the product.
  • the present invention provides an environmentally sound package that provides sufficient structural integrity and thermal insulation while reducing the overall quantity of adhesives to the substrates upon which it is being applied.
  • the present invention relates to a water-based resin emulsion composition and method of using the water-based resin emulsion composition, which provides a greater insulation while providing structural integrity.
  • the present invention relates to an adhesive composition and method of using a water-based resin emulsion composition, which provides a greater insulation while providing structural integrity.
  • the present invention further provides a multilayer-substrate article that comprises the water-based resin emulsion adhesive interposed between the two substrates.
  • an adhesive composition comprising (a) an emulsion-based polymer selected from the group consisting of vinyl acetate ethylene dispersion, polyvinyl acetate, polyvinyl acetate polyvinyl alcohol, dextrin stabilized polyvinyl acetate, polyvinyl acetate copolymers, vinyl acetate-ethylene copolymers, vinylacrylic, styrene acrylic, acrylic, styrene butyl rubber, polyurethane and mixtures thereof; (b) a plurality of microspheres; and optionally (c) water and (d) plasticizer.
  • the volume of the expanded adhesive is at least 200% greater than the dry volume of the unexpanded adhesive.
  • an adhesive composition comprising (a) an emulsion-based polymer selected from the group consisting of vinyl acetate ethylene dispersion, polyvinyl acetate, polyvinyl acetate polyvinyl alcohol, dextrin stabilized polyvinyl acetate, polyvinyl acetate copolymers, vinyl acetate-ethylene copolymers, vinylacrylic, styrene acrylic, acrylic, styrene butyl rubber, polyurethane and mixtures thereof; (b) a plurality of microspheres; and optionally (c) water and (d) plasticizer.
  • the volume of the expanded adhesive is at least 200% greater than the wet volume of the unexpanded adhesive.
  • Still another embodiment provides an article of manufacture, which is a multilayer substrate container that comprises a substrate and an adhesive composition interposed between the substrates.
  • the adhesive composition comprises (a) an emulsion-based polymer; (b) a plurality of microspheres; and optionally (c) water and (d) plasticizer.
  • the volume of the expanded adhesive of the article is at least 200% greater than the dry volume of the unexpanded adhesive.
  • FIG. 1 is a photograph of the adhesive in various states on a substrate: (a) wet adhesive on a paper substrate; (b) dried adhesive on the substrate; (c) expanded adhesive on the substrate; and (d) compressed adhesive on a substrate.
  • the present invention provides an adhesive composition and an article of manufacture comprising the adhesive composition, which provides a greater insulation while providing structural integrity to the article.
  • the adhesive and the article require less carbon footprint, e.g., heat and trees, than conventional hot melt adhesives and multilayer substrates with heavier basis weight substrates.
  • the present invention is based on the discovery that an adhesive composition with a plurality of expandable microspheres provides improved structural integrity and thermal insulation.
  • the adhesive compositions described herein may be useful in an article comprising multilayer substrates. Through the use of the inventive adhesive composition, a greater insulation space may be provided between the two substrates which it is attached at the point of adhesion. Such article containing the multilayer substrates avoids the need for a medium, and thus, is a more environmentally conscious product.
  • the insulating products useful herein include paper products for consumer use, such as for hot drinking cups and lids, cold drinking cups and lids, hot food containers and lids, cold food containers and lids, freezer cartons and cases, and the like.
  • the adhesive composition may be made from any number of materials. Desirably, the adhesive composition includes an emulsion polymer component, a plurality of microspheres, and optionally, plasticizer and water. The adhesive composition may further include one or more preservatives, tackifiers or fillers. Other materials that do not adversely affect the adhesive and insulating properties of the adhesive composition may be used as desired.
  • the adhesive composition includes an emulsion polymer component.
  • the emulsion polymer may be present in the adhesive composition in any amount, and desirably is present in an amount of from about 50% to about 99.5 wt %, preferably from about 50% to about 70 wt %, by weight of the adhesive composition prior to setting of the composition.
  • the solid levels vary from about 40 wt % to about 60 wt %, based on the emulsion polymer.
  • the emulsion polymer component may include any desired polymer components, including vinyl acetate ethylene dispersion, polyvinyl acetate, polyvinyl acetate polyvinyl alcohol, dextrin stabilized polyvinyl acetate, polyvinyl acetate copolymers, vinyl acetate ethylene copolymers, vinylacrylic, styrene acrylic, acrylic, styrene butyl rubber, polyurethane and mixtures thereof.
  • Particularly preferred emulsion polymer components are vinyl acetate ethylene dispersion and polyvinyl acetate.
  • the adhesive composition includes a plurality of pre-expanded or expandable microspheres.
  • the pre-expanded microspheres are fully expanded and do not need to undergo further expansion.
  • the expandable microspheres useful in the present invention should be capable of expanding in size in the presence of heat and/or radiation energy (including, for example, microwave, infrared, radiofrequency, and/or ultrasonic energy).
  • the microspheres useful in the present invention include, for example, heat expandable polymeric microspheres, including those having a hydrocarbon core and a polyacrylonitrile shell (such as those sold under the trade name DUALITE®) and other similar microspheres (such as those sold under the trade name EXPANCEL®).
  • the expandable microspheres may have any unexpanded size, including from about 12 microns to about 30 microns in diameter. In the presence of heat, the expandable microspheres of the present invention may be capable of increasing in diameter by about 3 times to about 10 times.
  • the adhesive composition becomes a foam-like material, which has improved insulation properties. It may be desired, the expansion of the microspheres takes place in a partially set adhesive composition.
  • the expandable microspheres have a particular temperature at which they begin to expand and a second temperature at which they have reached maximum expansion.
  • Different grades of microspheres have different expansion temperature (Texp) and maximum expansion temperature (Tmax).
  • Texp expansion temperature
  • Tmax maximum expansion temperature
  • one particularly useful microsphere has a Texp of about 80° C. and a Tmax of about 90° C. While any particular grade of microspheres may be used in the present invention, the Texp and Tmax of the microspheres should be taken into account when formulating and processing.
  • the temperature at which the microspheres have reached maximum expansion (Tmax) is desirably from about 120° C. to about 140° C.
  • the processing temperatures may be modified depending upon these temperatures.
  • these microspheres are able to move within the composition and are able to expand. Once the adhesive composition is fully dry, however, the microspheres are substantially locked in place, making expansion thereof difficult, if not impossible.
  • the expandable microspheres be present in the adhesive composition in an amount of from about 0.1% to about 10% by weight of the adhesive composition prior to setting of the composition, and more desirably from about 0.5% to about 7% by weight of the adhesive composition prior to setting of the composition, and most desirably at about 1% to about 5% by weight of the adhesive composition prior to setting of the composition.
  • the expansion ratio of the expandable microspheres and the loading level of the microspheres will be related to each other.
  • the amount of the expandable microspheres in the adhesive can be adjusted.
  • the desired amount of the microspheres in the composition may be modified.
  • the adhesive composition includes too high a concentration of expandable microspheres, there will be insufficient adhesion and strength upon expansion of the microspheres, and thereby weakening the structural integrity of the composite.
  • the dry volume of the expanded adhesive is at least 200% greater than the dry volume of the unexpanded adhesives. In preferred embodiments, it is desirable that the dry volume of the expanded adhesive is at least 400% greater than the dry volume of the unexpanded adhesives. In another embodiment, the dry volume of the expanded adhesive is at least 400% greater than the wet volume of the unexpanded adhesives. As shown in FIG. 1 , a 5 milligram (0.1 gift wet bead) wet adhesive dot ( FIG. 1 a ) on a substrate can expand to a height of about 2.2 mm ( FIG. 1 c ).
  • the expanded adhesive can maintain greater than 75% of its structural integrity of the bead height), even when compressed with a 2.6 psi pressure at 190° F. As shown in FIG. 1 d , the compressed adhesive maintained a height of 1.8 mm even after the hot compression.
  • the adhesive composition optionally includes a plasticizer.
  • plasticizers are dibenzoates available as BENZOFLEX®, such as diethylene glycol dibenzoate, dipropylene glycol dibenzoate, and the like.
  • the adhesive composition may optionally include any polar solvent, particularly water, in the formulation.
  • the adhesive composition optionally further includes any tackifiers, humectants, crosslinkers, preservatives, e.g., antioxidant, biocide; filler, pigment, dye, stabilizer, rheology modifier, polyvinyl alcohol, and mixtures thereof.
  • preservatives e.g., antioxidant, biocide
  • filler pigment, dye, stabilizer, rheology modifier, polyvinyl alcohol, and mixtures thereof.
  • a crosslinker will further increase the structural integrity of the adhesive after the microspheres are expanded.
  • These components can be included in an amount of from about 0.05% to about 15% by weight of the adhesive composition prior to setting of the composition.
  • Exemplary preservatives include 1,2-benzisothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one and 2-Methyl-4-isothiazolin-3-one.
  • preservatives may be used in the amount of from about 0.05% to about 0.5% by weight of the
  • the adhesive composition may further include an accelerator.
  • the accelerator is a multivalent cation from water-soluble salts, including commonly available aluminum nitrate (Al(NO 3 ) 3 ), zirconium acetate, ammonium zirconyl carbonate (available as Bacote 20 from Zirconium Chemicals).
  • Al(NO 3 ) 3 aluminum nitrate
  • zirconium acetate zirconium acetate
  • ammonium zirconyl carbonate available as Bacote 20 from Zirconium Chemicals.
  • the adhesive can start to coalesce at room temperature, the adhesive composition may still have high moisture content and will be substantially fluid.
  • a form of energy may be introduced to the adhesive to expand the microspheres before fully drying the adhesive. Partially drying the adhesive composition (i.e., leaving a higher amount of moisture in the adhesive, such as at least 10% moisture content) allows the expandable microspheres to expand.
  • the form of energy for expansion is typically heat from conduction, induction or radiation. For adhesives containing pre-expanded microspheres, no additional form of energy is necessary.
  • the adhesive composition may be applied to the surface (or surfaces) of a substrate and subjected to heat sufficient to coalesce the adhesive. At the onset of adhesive coalescence and while the adhesive is still substantially fluid-like, the adhesive may aid in holding the adhesive and microspheres in place, but will allow the microspheres the freedom to expand. In one embodiment, the heat may then be raised to a temperature sufficient to expand the microspheres. It is preferable for the heater to be set to a temperature range between the Texp and Tmax of the microspheres.
  • the heat may be raised again to a temperature sufficient to fully drive the water off the adhesive composition.
  • Heat may be applied by any desired method, including in an oven or through the use of heated rollers.
  • the various stages onset of setting, expansion of the microspheres, and fully drying the adhesive
  • induction heating method may be used in the process.
  • the process may include any combination of heat application and radiation application.
  • the initial coalescence of the adhesive may be achieved through direct heat, while the expansion of the microspheres may be achieved through application of radiation energy.
  • additives may be included in the composition to increase the coalescence of the adhesive, is desired.
  • the inventive adhesive is particularly suitable for insulative packages that are typically directed for use at elevated and/or reduced temperatures and requires thermal insulation.
  • Another embodiment provides a method of preparing an article having improved structural integrity and insulative properties, including the steps of: (a) providing a first substrate having a first side and second side; (b) providing a second substrate having a first side and second side; (c) preparing an adhesive composition by combining (i) an emulsion-based polymer selected from the group consisting of vinyl acetate ethylene dispersion, polyvinyl acetate, polyvinyl acetate polyvinyl alcohol, dextrin stabilized polyvinyl acetate, polyvinyl acetate copolymers, vinyl acetate-ethylene copolymers, vinylacrylic, styrene acrylic, acrylic, styrene butyl rubber, polyurethane and mixtures thereof; (ii) a plurality of expandable microspheres, and optionally (iii) a plasticizer and (iv) water to form an adhesive; (d) applying the adhesive either (i) to a surface of the first side of the first substrate, (
  • the adhesives may be formed immediately prior to applying onto a substrate or pre-made in advance and stored until needed.
  • Another embodiment is directed to insulated packages and a method for forming insulated packages.
  • the packages include cups, food containers, cases, cartons, bags, lids, boxes, envelopes, wraps, clamshells, and the like. It is particularly preferred that the substrates of the packages have a reduced basis weight, caliper, and fiber content as compared to traditional substrates used for the same packages.
  • the substrates include fibreboards, chipboards, corrugated boards, corrugated mediums, solid bleached boards (SBB), solid bleached sulphite boards (SBS), solid unbleached board (SLB), white lined chipboards (WLC), kraft papers, kraft boards, coated papers, binder boards, and oriented polypropylene films and reduced basis weight substrates.
  • SBB solid bleached boards
  • SBS solid bleached sulphite boards
  • SLB solid unbleached board
  • WLC white lined chipboards
  • kraft papers kraft boards
  • coated papers coated papers
  • binder boards and oriented polypropylene films and reduced basis weight substrates.
  • an insulating sheet including a substantially flat paper or film liner having a first side and a second side.
  • the first side of the paper or film liner includes a plurality of expandable microspheres secured thereto in an adhesive composition, where the plurality of expandable microspheres has been expanded and the adhesive composition has been dried.
  • the product includes a paper or film liner having an adhered, foam-like composition on the first side thereof.
  • the expandable microspheres include those described above, and the adhesive composition includes the components described above, including the emulsion polymer, and optional polar solvent, plasticizer, humectants, preservatives, or fillers.
  • the adhesive composition may be applied to the first surface of the paper or film liner in any configuration desired, including in a series of dots, stripes, waves, checkerboard patterns, any general polyhedron shapes that have substantially flat bases, and combinations thereof Application of these patterns decreases the amount of adhesive in the packages. Further, the adhesive composition may be applied to the first surface in a series of cylinders. In addition, if desired, the adhesive composition may be applied to the first surface as a substantially flat sheet of adhesive covering the entire first surface (full lamination) or covering a portion of the first surface. The adhesive composition may be applied in the presence of heat if desired; however, it is important that the heat at application not be so high as to fully set the adhesive composition before expanding the expandable microspheres.
  • a second paper or film liner may be applied to the top surface of the adhesive composition, forming a sandwiched configuration of: first paper or film liner—adhesive with expanded microspheres—second paper or film liner.
  • the paper or film liner is then exposed to heat and/or radiation energy sufficient to expand the plurality of microspheres.
  • the paper or film liner with wet adhesive thereon is exposed to heat at a temperature sufficient to expand at least a majority of the microspheres, in between the ranges of Texp and Tmax.
  • the paper or film liner with wet adhesive thereon is exposed to microwave or infrared energy sufficient to expand at least a majority of the expandable microspheres.
  • the resulting product is a paper or film liner having an adhesive having expanded microspheres therein.
  • the adhesive composition may then be exposed to heat and/or radiation energy sufficient to fully set the adhesive composition.
  • a second paper or film liner having a first side and second side may be provided and the first side of the second paper or film liner applied to the surface of the applied adhesive composition, forming a sandwich configuration. Thereafter, expansion of the microspheres and setting of the adhesive may take place as explained above.
  • Multilayer substrate packages formed with the inventive adhesives containing microspheres improve the ability of the package to withstand strain under a constant stress at elevated temperatures. It is expected to those skilled in the art that the strain of the adhesive increases with the addition of microspheres at elevated temperature.
  • the inventive adhesive is particularly suitable for consumer packages that are typically directed for use at elevated and/or reduced temperatures.
  • the inventive adhesive provides structural support in between the paper boards of the package, and this maintains the structural integrity of the package, and thereby insulation is improved for the package.
  • a multilayer substrate that contains two substrates and the adhesive, without any further substrates, e.g., a medium.
  • the adhesive may be applied to completely coat the two liners or in a selected or a random pattern.
  • the insulated article with patterned adhesive allows for gaps within the two liners.
  • the insulated article comprises a substantially flat substrate and a non-flat, rounded substrate.
  • the adhesive is applied either to the substantially flat substrate, the non-flat substrate, or to both substrates, to form the insulated article.
  • the adhesive may be applied to completely coat (full lamination) the surface of the substrate(s) or to selectively coat portions of the surface of the substrate(s).
  • the pattern can be random or various ordered designs.
  • the resulting article thus has an insulating space between the liner surfaces.
  • the articles with patterned adhesives mimic medium structure of interposed between the two substrates. The space between the two substrates are generated and maintained by the adhesive.
  • Another exemplary consumer package is a corrugated box package formed with lower basis weight liner and medium.
  • the substrates are made of paper that has a reduced basis weight when compared to traditional insulating corrugated boards.
  • An adhesive composition was prepared having the following composition:
  • Component Component Wt. % Water-soluble resin Polyvinyl acetate stabilized 63 emulsion with polyvinyl alcohol, with a solids content of 56% Water-soluble resin Polyvinyl acetate stabilized 30 emulsion with dextrin, with a solids content of 63% Expandable microspheres DUALITE ® U020-125W 3 Plasticizer Glycerine 4
  • the above components were mixed in a vessel and then applied in between two paper substrates as thin, bead stripes of 0.1 g/ft to form a composite.
  • the bead stripes were expanded by microwave heating.
  • a comparative composite was made in the same manner, maintaining the same fly separation as the composite, but without any adhesive stripes as support.
  • the composite with the inventive adhesive retained heat better than the comparative composite.
  • the expanded adhesive can maintain its structural integrity even during hot compression.
  • a compression of 2.6 psi at 190° F. is applied to a bead height of 2.4 mm for 60 seconds by Texture Analyzer ( FIG. 1 c ).
  • the bead maintained greater than 75% of bead height, and the final height after the compression was 1.8 mm (see FIG. 1 d ).

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Abstract

An adhesive composition that provides improved structural integrity and insulative properties when applied to a substrate is provided. The adhesive composition includes an emulsion-based polymer, a plurality of microspheres; and optionally, water and plasticizer.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS
The application is a divisional of U.S. Non-Provisional patent application Ser. No. 14/092,110 filed Nov. 27, 2013, which is a continuation-in-part of U.S. Non-Provisional patent application Ser. No. 13/775,348 filed Feb. 25, 2013, which is a continuation of International Patent Application No. PCT/US2011/050965 filed Sep. 9, 2011, which claims the benefit of U.S. Provisional Patent Application No. 61/381,642 filed Sep. 10, 2010, the contents of all of which are incorporated herein by reference. The application is also a divisional of U.S. Non-Provisional patent application Ser. No. 14/092,110 filed Nov. 27, 2013, which is a continuation-in-part of U.S. Non-Provisional patent application Ser. No. 13/826,451 filed Mar. 14, 2013, which claims the benefit of U.S. Provisional Patent Application No. 61/706,447 filed Sep. 27, 2012, the contents of both of which are incorporated herein by reference.
FIELD OF THE INVENTION
The present invention relates to an adhesive composition having improved insulative properties while maintaining structural integrity when applied onto a package. In particular, the invention includes an adhesive composition and method of making an adhesive composition in providing insulation to multilayer substrates.
BACKGROUND OF THE INVENTION
Multilayer substrate articles comprise individual substrates bonded together with adhesives. Typically, cellulosic sheet, e.g., paperboard, cardboard, paper, coated paper, films, are bonded together with waterborne adhesives to form containers for consumer products such as cups, food containers, cases, cartons, bags, boxes, envelopes, wraps, lids, clamshells, and the like. Other non-multilayer substrate articles provide sufficient insulation but they are plastic based, e.g., polyurethanes, polystyrenes, and are considered as environmentally unsound,
While typical adhesives, such as hot melt adhesives, are sufficient to adhere the various layers of the insulating paper together, these adhesives do not act as insulation themselves. Also, in order to improve the strength of low basis weight substrates, Adhesive Level Effect on Corrugated Board Strength-Experiment and FE Modeling teaches to increase the amount of adhesives interposed between the substrates. However, increasing the amount of the adhesive in the article lengthens the drying time and thereby decreases manufacturing speed. Long drying time or heaters must be used to drive the water out of the substrates, which increases energy consumption.
The present invention seeks to improve insulating substrates, through the use of an adhesive composition that adds insulative properties to the product. The present invention provides an environmentally sound package that provides sufficient structural integrity and thermal insulation while reducing the overall quantity of adhesives to the substrates upon which it is being applied.
The present invention relates to a water-based resin emulsion composition and method of using the water-based resin emulsion composition, which provides a greater insulation while providing structural integrity.
SUMMARY OF THE INVENTION
The present invention relates to an adhesive composition and method of using a water-based resin emulsion composition, which provides a greater insulation while providing structural integrity. The present invention further provides a multilayer-substrate article that comprises the water-based resin emulsion adhesive interposed between the two substrates.
In a first embodiment, there is provided an adhesive composition comprising (a) an emulsion-based polymer selected from the group consisting of vinyl acetate ethylene dispersion, polyvinyl acetate, polyvinyl acetate polyvinyl alcohol, dextrin stabilized polyvinyl acetate, polyvinyl acetate copolymers, vinyl acetate-ethylene copolymers, vinylacrylic, styrene acrylic, acrylic, styrene butyl rubber, polyurethane and mixtures thereof; (b) a plurality of microspheres; and optionally (c) water and (d) plasticizer. The volume of the expanded adhesive is at least 200% greater than the dry volume of the unexpanded adhesive.
In another embodiment, there is provided an adhesive composition comprising (a) an emulsion-based polymer selected from the group consisting of vinyl acetate ethylene dispersion, polyvinyl acetate, polyvinyl acetate polyvinyl alcohol, dextrin stabilized polyvinyl acetate, polyvinyl acetate copolymers, vinyl acetate-ethylene copolymers, vinylacrylic, styrene acrylic, acrylic, styrene butyl rubber, polyurethane and mixtures thereof; (b) a plurality of microspheres; and optionally (c) water and (d) plasticizer. The volume of the expanded adhesive is at least 200% greater than the wet volume of the unexpanded adhesive.
Still another embodiment provides an article of manufacture, which is a multilayer substrate container that comprises a substrate and an adhesive composition interposed between the substrates. The adhesive composition comprises (a) an emulsion-based polymer; (b) a plurality of microspheres; and optionally (c) water and (d) plasticizer. The volume of the expanded adhesive of the article is at least 200% greater than the dry volume of the unexpanded adhesive.
BRIEF DESCRIPTION OF THE FIGURE
FIG. 1 is a photograph of the adhesive in various states on a substrate: (a) wet adhesive on a paper substrate; (b) dried adhesive on the substrate; (c) expanded adhesive on the substrate; and (d) compressed adhesive on a substrate.
 DETAILED DESCRIPTION OF THE INVENTION
The present invention provides an adhesive composition and an article of manufacture comprising the adhesive composition, which provides a greater insulation while providing structural integrity to the article. The adhesive and the article require less carbon footprint, e.g., heat and trees, than conventional hot melt adhesives and multilayer substrates with heavier basis weight substrates.
The present invention is based on the discovery that an adhesive composition with a plurality of expandable microspheres provides improved structural integrity and thermal insulation. The adhesive compositions described herein may be useful in an article comprising multilayer substrates. Through the use of the inventive adhesive composition, a greater insulation space may be provided between the two substrates which it is attached at the point of adhesion. Such article containing the multilayer substrates avoids the need for a medium, and thus, is a more environmentally conscious product. The insulating products useful herein include paper products for consumer use, such as for hot drinking cups and lids, cold drinking cups and lids, hot food containers and lids, cold food containers and lids, freezer cartons and cases, and the like.
The adhesive composition may be made from any number of materials. Desirably, the adhesive composition includes an emulsion polymer component, a plurality of microspheres, and optionally, plasticizer and water. The adhesive composition may further include one or more preservatives, tackifiers or fillers. Other materials that do not adversely affect the adhesive and insulating properties of the adhesive composition may be used as desired.
The adhesive composition includes an emulsion polymer component. The emulsion polymer may be present in the adhesive composition in any amount, and desirably is present in an amount of from about 50% to about 99.5 wt %, preferably from about 50% to about 70 wt %, by weight of the adhesive composition prior to setting of the composition. Depending on the emulsion polymer, the solid levels vary from about 40 wt % to about 60 wt %, based on the emulsion polymer. The emulsion polymer component may include any desired polymer components, including vinyl acetate ethylene dispersion, polyvinyl acetate, polyvinyl acetate polyvinyl alcohol, dextrin stabilized polyvinyl acetate, polyvinyl acetate copolymers, vinyl acetate ethylene copolymers, vinylacrylic, styrene acrylic, acrylic, styrene butyl rubber, polyurethane and mixtures thereof. Particularly preferred emulsion polymer components are vinyl acetate ethylene dispersion and polyvinyl acetate.
The adhesive composition includes a plurality of pre-expanded or expandable microspheres. The pre-expanded microspheres are fully expanded and do not need to undergo further expansion. The expandable microspheres useful in the present invention should be capable of expanding in size in the presence of heat and/or radiation energy (including, for example, microwave, infrared, radiofrequency, and/or ultrasonic energy). The microspheres useful in the present invention include, for example, heat expandable polymeric microspheres, including those having a hydrocarbon core and a polyacrylonitrile shell (such as those sold under the trade name DUALITE®) and other similar microspheres (such as those sold under the trade name EXPANCEL®). The expandable microspheres may have any unexpanded size, including from about 12 microns to about 30 microns in diameter. In the presence of heat, the expandable microspheres of the present invention may be capable of increasing in diameter by about 3 times to about 10 times. Upon expansion of the microspheres in the adhesive composition, the adhesive composition becomes a foam-like material, which has improved insulation properties. It may be desired, the expansion of the microspheres takes place in a partially set adhesive composition.
The expandable microspheres have a particular temperature at which they begin to expand and a second temperature at which they have reached maximum expansion. Different grades of microspheres have different expansion temperature (Texp) and maximum expansion temperature (Tmax). For example, one particularly useful microsphere has a Texp of about 80° C. and a Tmax of about 90° C. While any particular grade of microspheres may be used in the present invention, the Texp and Tmax of the microspheres should be taken into account when formulating and processing. The temperature at which the microspheres have reached maximum expansion (Tmax) is desirably from about 120° C. to about 140° C.
Although the choice of the particular microspheres and their respective Texp and Tmax is not critical to the invention, the processing temperatures may be modified depending upon these temperatures. Before the adhesive composition is fully dried, these microspheres are able to move within the composition and are able to expand. Once the adhesive composition is fully dry, however, the microspheres are substantially locked in place, making expansion thereof difficult, if not impossible.
In preferred embodiments, it is desirable that the expandable microspheres be present in the adhesive composition in an amount of from about 0.1% to about 10% by weight of the adhesive composition prior to setting of the composition, and more desirably from about 0.5% to about 7% by weight of the adhesive composition prior to setting of the composition, and most desirably at about 1% to about 5% by weight of the adhesive composition prior to setting of the composition. The expansion ratio of the expandable microspheres and the loading level of the microspheres will be related to each other.
Depending on the fully expanded size of the microspheres, the amount of the expandable microspheres in the adhesive can be adjusted. Depending upon the particular expandable microspheres used in the composition, the desired amount of the microspheres in the composition may be modified. Typically, if the adhesive composition includes too high a concentration of expandable microspheres, there will be insufficient adhesion and strength upon expansion of the microspheres, and thereby weakening the structural integrity of the composite.
It has been discovered that the addition of 0.1% to about 10% of expandable microspheres by weight of the adhesive composition prior to setting allows for improved structural integrity. The dry volume of the expanded adhesive is at least 200% greater than the dry volume of the unexpanded adhesives. In preferred embodiments, it is desirable that the dry volume of the expanded adhesive is at least 400% greater than the dry volume of the unexpanded adhesives. In another embodiment, the dry volume of the expanded adhesive is at least 400% greater than the wet volume of the unexpanded adhesives. As shown in FIG. 1, a 5 milligram (0.1 gift wet bead) wet adhesive dot (FIG. 1a ) on a substrate can expand to a height of about 2.2 mm (FIG. 1c ). The expanded adhesive can maintain greater than 75% of its structural integrity of the bead height), even when compressed with a 2.6 psi pressure at 190° F. As shown in FIG. 1d , the compressed adhesive maintained a height of 1.8 mm even after the hot compression.
The adhesive composition optionally includes a plasticizer. Exemplary plasticizers are dibenzoates available as BENZOFLEX®, such as diethylene glycol dibenzoate, dipropylene glycol dibenzoate, and the like.
The adhesive composition may optionally include any polar solvent, particularly water, in the formulation.
The adhesive composition optionally further includes any tackifiers, humectants, crosslinkers, preservatives, e.g., antioxidant, biocide; filler, pigment, dye, stabilizer, rheology modifier, polyvinyl alcohol, and mixtures thereof. The addition of a crosslinker will further increase the structural integrity of the adhesive after the microspheres are expanded. These components can be included in an amount of from about 0.05% to about 15% by weight of the adhesive composition prior to setting of the composition. Exemplary preservatives include 1,2-benzisothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one and 2-Methyl-4-isothiazolin-3-one. Typically, preservatives may be used in the amount of from about 0.05% to about 0.5% by weight of the adhesive composition prior to setting of the composition.
The adhesive composition may further include an accelerator. The accelerator is a multivalent cation from water-soluble salts, including commonly available aluminum nitrate (Al(NO3)3), zirconium acetate, ammonium zirconyl carbonate (available as Bacote 20 from Zirconium Chemicals). The addition of a multivalent water-soluble salt shortens the time required for radiation during the expansion of the adhesive composition.
Although the adhesive can start to coalesce at room temperature, the adhesive composition may still have high moisture content and will be substantially fluid. For adhesives with expandable microspheres, a form of energy may be introduced to the adhesive to expand the microspheres before fully drying the adhesive. Partially drying the adhesive composition (i.e., leaving a higher amount of moisture in the adhesive, such as at least 10% moisture content) allows the expandable microspheres to expand. The form of energy for expansion is typically heat from conduction, induction or radiation. For adhesives containing pre-expanded microspheres, no additional form of energy is necessary.
For both expandable and pre-expanded microsphere containing adhesives, heaters and fans may be used to drive off the excess water to aid in drying the adhesives. In a particularly desirable embodiment of manufacturing products, the adhesive composition may be applied to the surface (or surfaces) of a substrate and subjected to heat sufficient to coalesce the adhesive. At the onset of adhesive coalescence and while the adhesive is still substantially fluid-like, the adhesive may aid in holding the adhesive and microspheres in place, but will allow the microspheres the freedom to expand. In one embodiment, the heat may then be raised to a temperature sufficient to expand the microspheres. It is preferable for the heater to be set to a temperature range between the Texp and Tmax of the microspheres. Finally, the heat may be raised again to a temperature sufficient to fully drive the water off the adhesive composition. Heat may be applied by any desired method, including in an oven or through the use of heated rollers. It should be noted that the various stages (onset of setting, expansion of the microspheres, and fully drying the adhesive) may be achieved by radiation energy, either as a replacement for, or in addition to, direct heat. That is, for example, the various steps may be achieved by use of microwave or radiofrequency radiation. Besides conduction, induction heating method may be used in the process. In addition, the process may include any combination of heat application and radiation application. For example, the initial coalescence of the adhesive may be achieved through direct heat, while the expansion of the microspheres may be achieved through application of radiation energy.
Other additives may be included in the composition to increase the coalescence of the adhesive, is desired.
The inventive adhesive is particularly suitable for insulative packages that are typically directed for use at elevated and/or reduced temperatures and requires thermal insulation.
Another embodiment provides a method of preparing an article having improved structural integrity and insulative properties, including the steps of: (a) providing a first substrate having a first side and second side; (b) providing a second substrate having a first side and second side; (c) preparing an adhesive composition by combining (i) an emulsion-based polymer selected from the group consisting of vinyl acetate ethylene dispersion, polyvinyl acetate, polyvinyl acetate polyvinyl alcohol, dextrin stabilized polyvinyl acetate, polyvinyl acetate copolymers, vinyl acetate-ethylene copolymers, vinylacrylic, styrene acrylic, acrylic, styrene butyl rubber, polyurethane and mixtures thereof; (ii) a plurality of expandable microspheres, and optionally (iii) a plasticizer and (iv) water to form an adhesive; (d) applying the adhesive either (i) to a surface of the first side of the first substrate, (ii) to a surface of the second side of the second substrate or (iii) to both a surface of the first side of the first substrate and a surface of the second side of the second substrate; (e) contacting the first substrate and the second substrate together where the applied adhesive is interposed between the two substrates to form a composite structure; and (f) applying heat and/or radiation to expand the expandable microspheres to form a bond adhering the first and the second substrates together. The resultant multilayer substrate with an adhesive containing the microspheres has an improved structural integrity and thermal insulation.
The adhesives may be formed immediately prior to applying onto a substrate or pre-made in advance and stored until needed.
Another embodiment is directed to insulated packages and a method for forming insulated packages. The packages include cups, food containers, cases, cartons, bags, lids, boxes, envelopes, wraps, clamshells, and the like. It is particularly preferred that the substrates of the packages have a reduced basis weight, caliper, and fiber content as compared to traditional substrates used for the same packages.
The substrates include fibreboards, chipboards, corrugated boards, corrugated mediums, solid bleached boards (SBB), solid bleached sulphite boards (SBS), solid unbleached board (SLB), white lined chipboards (WLC), kraft papers, kraft boards, coated papers, binder boards, and oriented polypropylene films and reduced basis weight substrates.
In one embodiment, there is provided an insulating sheet including a substantially flat paper or film liner having a first side and a second side. The first side of the paper or film liner includes a plurality of expandable microspheres secured thereto in an adhesive composition, where the plurality of expandable microspheres has been expanded and the adhesive composition has been dried. Thus, the product includes a paper or film liner having an adhered, foam-like composition on the first side thereof. The expandable microspheres include those described above, and the adhesive composition includes the components described above, including the emulsion polymer, and optional polar solvent, plasticizer, humectants, preservatives, or fillers.
The adhesive composition may be applied to the first surface of the paper or film liner in any configuration desired, including in a series of dots, stripes, waves, checkerboard patterns, any general polyhedron shapes that have substantially flat bases, and combinations thereof Application of these patterns decreases the amount of adhesive in the packages. Further, the adhesive composition may be applied to the first surface in a series of cylinders. In addition, if desired, the adhesive composition may be applied to the first surface as a substantially flat sheet of adhesive covering the entire first surface (full lamination) or covering a portion of the first surface. The adhesive composition may be applied in the presence of heat if desired; however, it is important that the heat at application not be so high as to fully set the adhesive composition before expanding the expandable microspheres. A skilled artisan can determine this amount of pressure without undue experimentation. Optionally, a second paper or film liner may be applied to the top surface of the adhesive composition, forming a sandwiched configuration of: first paper or film liner—adhesive with expanded microspheres—second paper or film liner.
After the adhesive begins to coalesce, the paper or film liner is then exposed to heat and/or radiation energy sufficient to expand the plurality of microspheres. In one embodiment, the paper or film liner with wet adhesive thereon is exposed to heat at a temperature sufficient to expand at least a majority of the microspheres, in between the ranges of Texp and Tmax. In another embodiment, the paper or film liner with wet adhesive thereon is exposed to microwave or infrared energy sufficient to expand at least a majority of the expandable microspheres. The resulting product is a paper or film liner having an adhesive having expanded microspheres therein. The adhesive composition may then be exposed to heat and/or radiation energy sufficient to fully set the adhesive composition.
If desired, after application of the adhesive composition to the first side of the paper or film liner, a second paper or film liner having a first side and second side may be provided and the first side of the second paper or film liner applied to the surface of the applied adhesive composition, forming a sandwich configuration. Thereafter, expansion of the microspheres and setting of the adhesive may take place as explained above.
Multilayer substrate packages formed with the inventive adhesives containing microspheres improve the ability of the package to withstand strain under a constant stress at elevated temperatures. It is expected to those skilled in the art that the strain of the adhesive increases with the addition of microspheres at elevated temperature. The inventive adhesive is particularly suitable for consumer packages that are typically directed for use at elevated and/or reduced temperatures. The inventive adhesive provides structural support in between the paper boards of the package, and this maintains the structural integrity of the package, and thereby insulation is improved for the package.
In one embodiment, there is provided a multilayer substrate that contains two substrates and the adhesive, without any further substrates, e.g., a medium. Heretofore, it has been difficult to achieve a product that has the necessary thermal insulation and structural integrity without including a medium layer. The adhesive may be applied to completely coat the two liners or in a selected or a random pattern. The insulated article with patterned adhesive allows for gaps within the two liners.
Yet in another embodiment, the insulated article comprises a substantially flat substrate and a non-flat, rounded substrate. The adhesive is applied either to the substantially flat substrate, the non-flat substrate, or to both substrates, to form the insulated article. The adhesive may be applied to completely coat (full lamination) the surface of the substrate(s) or to selectively coat portions of the surface of the substrate(s). The pattern can be random or various ordered designs. The resulting article thus has an insulating space between the liner surfaces. The articles with patterned adhesives mimic medium structure of interposed between the two substrates. The space between the two substrates are generated and maintained by the adhesive.
Another exemplary consumer package is a corrugated box package formed with lower basis weight liner and medium. The substrates are made of paper that has a reduced basis weight when compared to traditional insulating corrugated boards.
The present invention may be better understood through analysis of the following examples, which are non-limiting and are intended only to help explain the invention.
EXAMPLES Example 1 Formation of an Adhesive with Improved Insulating Properties
An adhesive composition was prepared having the following composition:
Component Component Wt. %
Water-soluble resin Polyvinyl acetate stabilized 63
emulsion with polyvinyl alcohol, with
a solids content of 56%
Water-soluble resin Polyvinyl acetate stabilized 30
emulsion with dextrin, with a solids
content of 63%
Expandable microspheres DUALITE ® U020-125W 3
Plasticizer Glycerine 4
The above components were mixed in a vessel and then applied in between two paper substrates as thin, bead stripes of 0.1 g/ft to form a composite. The bead stripes were expanded by microwave heating. A comparative composite was made in the same manner, maintaining the same fly separation as the composite, but without any adhesive stripes as support.
Both composites were tested for their insulative properties with a thermal imaging technique (Infrared Cameras Inc.'s ICI-7320 USB camera and the accompanying IR Flash software (version 2.12.12.7). A 190° F. heat source was placed on one side of the composite and the surface temperature of the composite was monitored from the opposite side. The surface temperature of the composite and comparative composite with its corresponding time are shown in the following table.
Time Comparative
Lapsed, composite Composite Temperature
seconds (° F.) (° F.) difference
0 77.6 78.1 −0.5
1 77.7 78.2 −0.5
2 78.4 78.4 0.0
3 79.3 79.1 0.1
4 81.0 79.7 1.3
5 90.9 82.0 8.9
6 100.4 88.8 11.6
7 109.0 97.1 11.9
8 116.7 104.9 11.8
9 122.9 111.5 11.4
10 128.0 117.3 10.7
As shown above, the composite with the inventive adhesive retained heat better than the comparative composite.
Example 2 Structural Integrity
The expanded adhesive can maintain its structural integrity even during hot compression. As shown in FIG. 1, a compression of 2.6 psi at 190° F. is applied to a bead height of 2.4 mm for 60 seconds by Texture Analyzer (FIG. 1c ). The bead maintained greater than 75% of bead height, and the final height after the compression was 1.8 mm (see FIG. 1d ).

Claims (11)

The invention claimed is:
1. An article comprising a first substrate, a second substrate, and an adhesive composition interposed between the two substrates comprising:
(a) about 50 to about 99.9 weight percent, on a dry weight basis, of an emulsion-based polymer selected from the group consisting of vinyl acetate ethylene dispersion, polyvinyl acetate, polyvinyl acetate polyvinyl alcohol, dextrin stabilized polyvinyl acetate, polyvinyl acetate copolymers, vinyl acetate-ethylene copolymers, vinylacrylic, styrene acrylic, acrylic, styrene butyl rubber, polyurethane and mixtures thereof;
(b) about 0.1 to about 10 weight percent, on a dry weight basis, of a plurality of expandable microspheres;
(c) water; and
(d) optionally, plasticizer and/or preservative;
wherein the volume of the microspheres is greater than 200% in the dry adhesive upon expanding the microsphere.
2. The article of claim 1 wherein the first and the second substrate are selected from the group consisting of fiberboard, corrugated board, solid bleached boards, kraft paper, coated paper or oriented polypropylene film.
3. The article of claim 2 wherein the first and the second substrate are haft paper or coated paper.
4. The article of claim 2 wherein the boards and papers comprise a portion of recycled fiber.
5. The article of claim 1, wherein the emulsion-based polymer is selected from the group consisting of vinyl acetate ethylene dispersion, polyvinyl acetate.
6. The article of claim 1, wherein the plurality of microspheres are present in an amount of from about 0.5 wt % to about 5 wt %, based on the total (wet) weight of the adhesive.
7. The article of claim 6, wherein the microspheres are expandable polymeric microspheres.
8. The article of claim 1, wherein the adhesive further comprises a crosslinker, filler, pigment, dye, stabilizer, rheology modifier, polyvinyl alcohol, humectant and the mixtures thereof.
9. The article of claim 1, wherein the adhesive further comprises an accelerator that is a multivalent water-soluble salt.
10. The article of claim 9, wherein the accelerator is selected from the group consisting of aluminum nitrate, zirconium acetate, ammonium zirconyl carbonate and mixtures thereof.
11. The article of claim 1, which is selected from the group consisting of a cup, food container, case, carton, bag, box, lid, envelope, wrap or clamshell.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11773297B2 (en) 2017-07-18 2023-10-03 Henkel Ag & Co., Kgaa Dielectric heating of foamable compositions
US11833788B2 (en) 2018-02-16 2023-12-05 Henkel Ag & Co, Kgaa Method for producing a multi-layer substrate
US11926134B2 (en) 2017-08-25 2024-03-12 Henkel Ag & Co. Kgaa Process for forming improved protective eco-friendly pouch and packaging and products made therefrom
US11970634B2 (en) 2012-09-27 2024-04-30 Henkel Ag & Co. Kgaa Waterborne adhesives for reduced basis weight multilayer substrates and use thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130303351A1 (en) 2006-04-03 2013-11-14 Lbp Manufacturing, Inc. Microwave heating of heat-expandable materials for making packaging substrates and products
ES2644773T1 (en) * 2014-11-04 2017-11-30 Sca Forest Products Ab Intermediate laminated product, expanded laminated structure and manufacturing process thereof
US10787303B2 (en) 2016-05-29 2020-09-29 Cellulose Material Solutions, LLC Packaging insulation products and methods of making and using same
US11078007B2 (en) 2016-06-27 2021-08-03 Cellulose Material Solutions, LLC Thermoplastic packaging insulation products and methods of making and using same
JP6810571B2 (en) * 2016-10-05 2021-01-06 大王製紙株式会社 Manufacturing method of sheet for heat insulating container
US10501252B1 (en) * 2017-07-27 2019-12-10 Amazon Technologies, Inc. Packaging material having patterns of microsphere adhesive members that allow for bending around objects
CN108102599A (en) * 2018-01-30 2018-06-01 陈良地 A kind of fire protection flame retarding corrugated board and its preparation process
US11952190B2 (en) * 2019-03-29 2024-04-09 Gpcp Ip Holdings Llc Removeable band for stack of disposable cutlery
EP3822056B1 (en) 2019-11-18 2024-05-08 Heraeus Noblelight Ltd. System for treatment of a multi-layered cushioning product and operating method for a system for expanding a multi-layered cushioning product
CN115298250A (en) * 2020-06-22 2022-11-04 汉高股份有限及两合公司 Hybrid expandable composition and use thereof
US20240317955A1 (en) * 2021-02-01 2024-09-26 3M Innovative Properties Company Foamed compositions, foam padded materials, and packaging articles
WO2022165304A1 (en) * 2021-02-01 2022-08-04 3M Innovative Properties Company Foamed compositions, foam padded materials, and packaging articles
WO2024020012A1 (en) * 2022-07-18 2024-01-25 Georgia-Pacific Corrugated Llc Starch-based padding for roll stock and padded mailers and method of making the same

Citations (78)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2998501A (en) 1957-12-27 1961-08-29 Koppers Co Inc Apparatus for making foamed polymeric structural materials
US3253064A (en) 1962-04-17 1966-05-24 Robert B Buonaiuto Process for molding a foamed plastic having an outermost uniform skin
US3401475A (en) 1966-07-18 1968-09-17 Dow Chemical Co Label and labelled container
US3563851A (en) 1965-04-26 1971-02-16 Nat Starch Chem Corp Water resistant vinyl acetate copolymer adhesive compositions
US3615972A (en) 1967-04-28 1971-10-26 Dow Chemical Co Expansible thermoplastic polymer particles containing volatile fluid foaming agent and method of foaming the same
US4005033A (en) * 1973-05-17 1977-01-25 Champion International Corporation Resilient organic microspheres in mastic adhesives, sealants, caulks, coating compounds and related products, and methods of manufacture
US4006273A (en) 1975-02-03 1977-02-01 Pratt & Lambert, Inc. Washable and dry-cleanable raised printing on fabrics
US4094685A (en) * 1976-07-23 1978-06-13 Polymerics, Inc. Expandable polymeric coating compositions
US4350788A (en) 1980-09-26 1982-09-21 Nippon Gohsei Kagaku Kogyo Kabushiki Kaisha Synthetic resin emulsion and its uses
US4483889A (en) 1982-08-05 1984-11-20 Kemanord Ab Method for the production of fibre composite materials impregnated with resin
JPS6144965A (en) 1984-08-10 1986-03-04 Matsushita Refrig Co Expandable adhesive
WO1990014223A1 (en) 1989-05-22 1990-11-29 Nordson Corporation Method of bonding with water-based adhesives
US5114509A (en) 1985-05-21 1992-05-19 Battelle Memorial Institute Starch adhesive bonding
CA2078476A1 (en) 1991-09-24 1993-03-25 Frank Vito Distefano High performance solvent-free contact adhesive
JPH05239423A (en) 1991-09-20 1993-09-17 Natl Starch & Chem Investment Holding Corp Corrugating adhesive containing soluble high amylose starch
US5356683A (en) 1993-10-28 1994-10-18 Rohm And Haas Company Expandable coating composition
JPH06313163A (en) 1993-03-05 1994-11-08 Toppan Printing Co Ltd Heat-and pressure-sensitive adhesive composition and heat-and pressure-sensitive adhesive sheet
US5387626A (en) * 1991-09-03 1995-02-07 Hoechst Aktiengesellschaft Additive combination for improving the processing properties of water-containing mixtures of building materials
US5393336A (en) 1993-06-01 1995-02-28 National Starch And Chemical Investment Holding Corporation Water resistant high amylose corrugating adhesive with improved runnability
CA2145938A1 (en) 1994-04-06 1995-10-07 E. Chris Hornaman Construction adhesive composition
JPH08175576A (en) 1994-12-26 1996-07-09 The Box:Kk Heat-insulating package
US5542599A (en) 1995-08-07 1996-08-06 Sobol; Ronald E. Biodegradable thermally insulated beverage cup
JPH09164621A (en) 1995-10-11 1997-06-24 Sanko:Kk Heat insulating material made of paper
JPH09217050A (en) 1996-02-13 1997-08-19 Chuo Rika Kogyo Kk Waterborne adhesive composition
US5685480A (en) 1996-08-16 1997-11-11 Choi; Danny K. Insulated drinking cup
US5928741A (en) * 1992-08-11 1999-07-27 E. Khashoggi Industries, Llc Laminated articles of manufacture fashioned from sheets having a highly inorganically filled organic polymer matrix
US6139961A (en) 1998-05-18 2000-10-31 Rohm And Haas Company Hollow sphere organic pigment for paper or paper coatings
US6231970B1 (en) 2000-01-11 2001-05-15 E. Khashoggi Industries, Llc Thermoplastic starch compositions incorporating a particulate filler component
US6255369B1 (en) 1996-09-27 2001-07-03 National Starch & Chemical Investment Holding Corporation Water-resistant, viscosity stable, alkaline corrugating adhesive composition
JP2001207146A (en) 2000-01-26 2001-07-31 Saiden Chemical Industry Co Ltd Water-based adhesive composition
WO2001062986A1 (en) 2000-02-25 2001-08-30 Roberto Solis Castillo Lining for natural and synthetic fibrous materials and application method
WO2002000800A2 (en) 2000-06-23 2002-01-03 Solutia Inc. Acrylic adhesive compositions comprising acrylate microspheres
WO2002031077A2 (en) 2000-10-10 2002-04-18 Henkel Kommanditgesellschaft Auf Aktien Two component thermosettable compositions useful for producing structural reinforcing adhesives
US6379497B1 (en) 1996-09-20 2002-04-30 Fort James Corporation Bulk enhanced paperboard and shaped products made therefrom
US20020068139A1 (en) 2000-12-04 2002-06-06 Polak Brent T. Foamed starch structures & methods for making them
US20020071947A1 (en) 1999-12-09 2002-06-13 Nano-Tex, Llc Microcellular foam and foamed composite material
US20020094403A1 (en) 2000-10-23 2002-07-18 Matsushita Electric Works, Ltd. Laminate with a peelable top layer and method of peeling off the top layer from the laminate
JP2003154589A (en) 2001-11-20 2003-05-27 Toppan Printing Co Ltd Heat-expandable laminate and foamed paper container using the laminate
US6648955B1 (en) 2000-10-25 2003-11-18 National Starch And Chemical Investment Holding Corporation Corrugating adhesive
US20040033343A1 (en) 2002-06-12 2004-02-19 Comeau Dominic Hamel Mold-resistant corrugated carboard for void-forming structures and process
US6740373B1 (en) 1997-02-26 2004-05-25 Fort James Corporation Coated paperboards and paperboard containers having improved tactile and bulk insulation properties
US6749705B2 (en) 2001-11-15 2004-06-15 National Starch And Chemical Investment Holding Corporation Adhesive and use thereof
US6838187B2 (en) 2002-05-10 2005-01-04 National Starch And Chemical Investment Holding Corporation Water based adhesive composition with release properties
JP2005097816A (en) 2003-09-02 2005-04-14 Nagoya Oil Chem Co Ltd Flame retardant fiber sheet and molded product of the same
CN1643100A (en) 2002-04-12 2005-07-20 雷米工业有限公司 Starch-based glue paste compositions
EP1216146B1 (en) 1999-08-10 2005-10-19 Gruppo X Di X Gruppo S.R.L. Filmable material with characteristics selectively modifiable by administration of particular types of energy
WO2005110737A1 (en) 2004-04-14 2005-11-24 Avery Dennison Corporation Microsphere containing electron beam cured pressure-sensitive adhesive tapes and methods of making and using same
EP1634897A2 (en) 1996-11-12 2006-03-15 Air Products And Chemicals, Inc. Water borne pressure sensitive adhesive compositions for bonding of polyvinylchloride
EP1674543A1 (en) 2004-12-22 2006-06-28 Ricoh Company, Ltd. Heat-sensitive adhesive material
US20070009723A1 (en) 2004-08-20 2007-01-11 Masanori Ogawa Flame-retardant sheet and formed article therefrom
EP1780250A1 (en) 2005-11-01 2007-05-02 Rohm and Haas Company Aqueous polymer dispersions comprising stable epoxy groups
US20070155859A1 (en) 2006-01-04 2007-07-05 Zhengzhe Song Reactive polyurethane hot melt adhesive
WO2007091961A1 (en) 2006-02-10 2007-08-16 Akzo Nobel N.V. Microspheres
US20070224395A1 (en) 2006-03-24 2007-09-27 Rowitsch Robert W Sprayable water-based adhesive
US20070228134A1 (en) 2006-04-03 2007-10-04 Cook Matthew R Thermally activatable insulating packaging
WO2007135451A1 (en) 2006-05-19 2007-11-29 Innovia Films Limited Sealable, peelable film
WO2007142593A1 (en) 2006-06-08 2007-12-13 Akzo Nobel N.V. Microspheres
US20070287776A1 (en) 2006-06-08 2007-12-13 Akzo Nobel N.V. Microspheres
US7335279B2 (en) * 2000-01-26 2008-02-26 International Paper Company Low density paperboard articles
US20080118693A1 (en) 2006-11-17 2008-05-22 Bilski Lori A Method of making a microsphere transfer adhesive
WO2008084372A1 (en) 2007-01-05 2008-07-17 Lecce Pen Company Spa Method for manufacturing reduced-weight paper, thin cardboard and cardboard, and compounds obtained therewith
CN101263184A (en) 2005-09-14 2008-09-10 国家淀粉及化学投资控股公司 Novel water-based adhesives for industrial applications
CN101476265A (en) 2008-12-31 2009-07-08 鹅妈妈教育咨询（上海）有限公司 Zeolite corrugated cardboard, and manufacturing method and apparatus thereof
US20090280322A1 (en) 2006-06-20 2009-11-12 Daniels Michael P Adhesive compositions, adhesive articles and methods for making the same
US20090321508A1 (en) 2006-04-03 2009-12-31 Thomas Fu Insulating packaging
US20100012712A1 (en) 2008-07-21 2010-01-21 Dixie Consumer Products Llc Paper cup manufacture with microencapsulated adhesive
US20100136269A1 (en) 2005-11-01 2010-06-03 E. Khashoggi Industries, Llc Extruded fiber reinforced cementitious products having wood-like properties and ultrahigh strength and methods for making the same
US20100181015A1 (en) 2009-01-22 2010-07-22 Kohler Herbert B Method for moisture and temperature control in corrugating operation
JP2010202996A (en) 2009-03-02 2010-09-16 Daio Paper Corp Converted paper
US20110019121A1 (en) 2009-07-24 2011-01-27 Au Optronics Corp. Flat panel display module
US20110033398A1 (en) 2008-04-14 2011-02-10 Severine Cauvin Emulsions Of Boron Crosslinked Organopolysiloxanes And Their Use In Personal Care Compositions
US20120015162A1 (en) 2010-06-22 2012-01-19 Societe D'enduction Et De Flockage Resin-coated material and process for manufacturing same
US20120048450A1 (en) 2010-09-01 2012-03-01 Lbp Manufacturing, Inc. Process of expediting activation of heat-expandable adhesives/coatings used in making packaging substrates
US20120100289A1 (en) 2010-09-29 2012-04-26 Basf Se Insulating compositions comprising expanded particles and methods for application and use
US20130160945A1 (en) 2010-09-10 2013-06-27 Henkel Corporation Adhesive having insulative properties
US20130303351A1 (en) 2006-04-03 2013-11-14 Lbp Manufacturing, Inc. Microwave heating of heat-expandable materials for making packaging substrates and products
US20140131367A1 (en) 2012-11-14 2014-05-15 Pactiv LLC Multilayer article and method for making a multilayer article, blank, and insulating cup
JP6313163B2 (en) 2014-08-28 2018-04-18 Kddi株式会社 Message analysis apparatus, message analysis method, and computer program

Patent Citations (80)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2998501A (en) 1957-12-27 1961-08-29 Koppers Co Inc Apparatus for making foamed polymeric structural materials
US3253064A (en) 1962-04-17 1966-05-24 Robert B Buonaiuto Process for molding a foamed plastic having an outermost uniform skin
US3563851A (en) 1965-04-26 1971-02-16 Nat Starch Chem Corp Water resistant vinyl acetate copolymer adhesive compositions
US3401475A (en) 1966-07-18 1968-09-17 Dow Chemical Co Label and labelled container
US3615972A (en) 1967-04-28 1971-10-26 Dow Chemical Co Expansible thermoplastic polymer particles containing volatile fluid foaming agent and method of foaming the same
US4005033A (en) * 1973-05-17 1977-01-25 Champion International Corporation Resilient organic microspheres in mastic adhesives, sealants, caulks, coating compounds and related products, and methods of manufacture
US4006273A (en) 1975-02-03 1977-02-01 Pratt & Lambert, Inc. Washable and dry-cleanable raised printing on fabrics
US4094685A (en) * 1976-07-23 1978-06-13 Polymerics, Inc. Expandable polymeric coating compositions
US4350788A (en) 1980-09-26 1982-09-21 Nippon Gohsei Kagaku Kogyo Kabushiki Kaisha Synthetic resin emulsion and its uses
US4483889A (en) 1982-08-05 1984-11-20 Kemanord Ab Method for the production of fibre composite materials impregnated with resin
JPS6144965A (en) 1984-08-10 1986-03-04 Matsushita Refrig Co Expandable adhesive
US5114509A (en) 1985-05-21 1992-05-19 Battelle Memorial Institute Starch adhesive bonding
WO1990014223A1 (en) 1989-05-22 1990-11-29 Nordson Corporation Method of bonding with water-based adhesives
US5387626A (en) * 1991-09-03 1995-02-07 Hoechst Aktiengesellschaft Additive combination for improving the processing properties of water-containing mixtures of building materials
JPH05239423A (en) 1991-09-20 1993-09-17 Natl Starch & Chem Investment Holding Corp Corrugating adhesive containing soluble high amylose starch
CA2078476A1 (en) 1991-09-24 1993-03-25 Frank Vito Distefano High performance solvent-free contact adhesive
US5264467A (en) 1991-09-24 1993-11-23 Air Products And Chemicals, Inc. High performance solvent-free contact adhesive
US5928741A (en) * 1992-08-11 1999-07-27 E. Khashoggi Industries, Llc Laminated articles of manufacture fashioned from sheets having a highly inorganically filled organic polymer matrix
JPH06313163A (en) 1993-03-05 1994-11-08 Toppan Printing Co Ltd Heat-and pressure-sensitive adhesive composition and heat-and pressure-sensitive adhesive sheet
US5393336A (en) 1993-06-01 1995-02-28 National Starch And Chemical Investment Holding Corporation Water resistant high amylose corrugating adhesive with improved runnability
US5356683A (en) 1993-10-28 1994-10-18 Rohm And Haas Company Expandable coating composition
CA2145938A1 (en) 1994-04-06 1995-10-07 E. Chris Hornaman Construction adhesive composition
JPH08175576A (en) 1994-12-26 1996-07-09 The Box:Kk Heat-insulating package
US5542599A (en) 1995-08-07 1996-08-06 Sobol; Ronald E. Biodegradable thermally insulated beverage cup
JPH09164621A (en) 1995-10-11 1997-06-24 Sanko:Kk Heat insulating material made of paper
JPH09217050A (en) 1996-02-13 1997-08-19 Chuo Rika Kogyo Kk Waterborne adhesive composition
US5685480A (en) 1996-08-16 1997-11-11 Choi; Danny K. Insulated drinking cup
US6379497B1 (en) 1996-09-20 2002-04-30 Fort James Corporation Bulk enhanced paperboard and shaped products made therefrom
US6255369B1 (en) 1996-09-27 2001-07-03 National Starch & Chemical Investment Holding Corporation Water-resistant, viscosity stable, alkaline corrugating adhesive composition
EP1634897A2 (en) 1996-11-12 2006-03-15 Air Products And Chemicals, Inc. Water borne pressure sensitive adhesive compositions for bonding of polyvinylchloride
US6740373B1 (en) 1997-02-26 2004-05-25 Fort James Corporation Coated paperboards and paperboard containers having improved tactile and bulk insulation properties
US6139961A (en) 1998-05-18 2000-10-31 Rohm And Haas Company Hollow sphere organic pigment for paper or paper coatings
EP1216146B1 (en) 1999-08-10 2005-10-19 Gruppo X Di X Gruppo S.R.L. Filmable material with characteristics selectively modifiable by administration of particular types of energy
US20020071947A1 (en) 1999-12-09 2002-06-13 Nano-Tex, Llc Microcellular foam and foamed composite material
US6231970B1 (en) 2000-01-11 2001-05-15 E. Khashoggi Industries, Llc Thermoplastic starch compositions incorporating a particulate filler component
JP2001207146A (en) 2000-01-26 2001-07-31 Saiden Chemical Industry Co Ltd Water-based adhesive composition
US7335279B2 (en) * 2000-01-26 2008-02-26 International Paper Company Low density paperboard articles
WO2001062986A1 (en) 2000-02-25 2001-08-30 Roberto Solis Castillo Lining for natural and synthetic fibrous materials and application method
WO2002000800A2 (en) 2000-06-23 2002-01-03 Solutia Inc. Acrylic adhesive compositions comprising acrylate microspheres
WO2002031077A2 (en) 2000-10-10 2002-04-18 Henkel Kommanditgesellschaft Auf Aktien Two component thermosettable compositions useful for producing structural reinforcing adhesives
US20020094403A1 (en) 2000-10-23 2002-07-18 Matsushita Electric Works, Ltd. Laminate with a peelable top layer and method of peeling off the top layer from the laminate
US6648955B1 (en) 2000-10-25 2003-11-18 National Starch And Chemical Investment Holding Corporation Corrugating adhesive
US20020068139A1 (en) 2000-12-04 2002-06-06 Polak Brent T. Foamed starch structures & methods for making them
US6749705B2 (en) 2001-11-15 2004-06-15 National Starch And Chemical Investment Holding Corporation Adhesive and use thereof
JP2003154589A (en) 2001-11-20 2003-05-27 Toppan Printing Co Ltd Heat-expandable laminate and foamed paper container using the laminate
CN1643100A (en) 2002-04-12 2005-07-20 雷米工业有限公司 Starch-based glue paste compositions
US6838187B2 (en) 2002-05-10 2005-01-04 National Starch And Chemical Investment Holding Corporation Water based adhesive composition with release properties
US20040033343A1 (en) 2002-06-12 2004-02-19 Comeau Dominic Hamel Mold-resistant corrugated carboard for void-forming structures and process
JP2005097816A (en) 2003-09-02 2005-04-14 Nagoya Oil Chem Co Ltd Flame retardant fiber sheet and molded product of the same
WO2005110737A1 (en) 2004-04-14 2005-11-24 Avery Dennison Corporation Microsphere containing electron beam cured pressure-sensitive adhesive tapes and methods of making and using same
US20070009723A1 (en) 2004-08-20 2007-01-11 Masanori Ogawa Flame-retardant sheet and formed article therefrom
EP1674543A1 (en) 2004-12-22 2006-06-28 Ricoh Company, Ltd. Heat-sensitive adhesive material
CN101263184A (en) 2005-09-14 2008-09-10 国家淀粉及化学投资控股公司 Novel water-based adhesives for industrial applications
EP1780250A1 (en) 2005-11-01 2007-05-02 Rohm and Haas Company Aqueous polymer dispersions comprising stable epoxy groups
US20100136269A1 (en) 2005-11-01 2010-06-03 E. Khashoggi Industries, Llc Extruded fiber reinforced cementitious products having wood-like properties and ultrahigh strength and methods for making the same
US20070155859A1 (en) 2006-01-04 2007-07-05 Zhengzhe Song Reactive polyurethane hot melt adhesive
WO2007091961A1 (en) 2006-02-10 2007-08-16 Akzo Nobel N.V. Microspheres
US20070224395A1 (en) 2006-03-24 2007-09-27 Rowitsch Robert W Sprayable water-based adhesive
US20070228134A1 (en) 2006-04-03 2007-10-04 Cook Matthew R Thermally activatable insulating packaging
US20130303351A1 (en) 2006-04-03 2013-11-14 Lbp Manufacturing, Inc. Microwave heating of heat-expandable materials for making packaging substrates and products
US20090321508A1 (en) 2006-04-03 2009-12-31 Thomas Fu Insulating packaging
WO2007135451A1 (en) 2006-05-19 2007-11-29 Innovia Films Limited Sealable, peelable film
WO2007142593A1 (en) 2006-06-08 2007-12-13 Akzo Nobel N.V. Microspheres
US20070287776A1 (en) 2006-06-08 2007-12-13 Akzo Nobel N.V. Microspheres
US20090280322A1 (en) 2006-06-20 2009-11-12 Daniels Michael P Adhesive compositions, adhesive articles and methods for making the same
US20080118693A1 (en) 2006-11-17 2008-05-22 Bilski Lori A Method of making a microsphere transfer adhesive
US20100139878A1 (en) 2007-01-05 2010-06-10 Lecce Pen Company Spa Method for Manufacturing Reduced-Weight Paper, Thin Cardboard and Cardboard, and Compounds Obtained Therewith
WO2008084372A1 (en) 2007-01-05 2008-07-17 Lecce Pen Company Spa Method for manufacturing reduced-weight paper, thin cardboard and cardboard, and compounds obtained therewith
US20110033398A1 (en) 2008-04-14 2011-02-10 Severine Cauvin Emulsions Of Boron Crosslinked Organopolysiloxanes And Their Use In Personal Care Compositions
US20100012712A1 (en) 2008-07-21 2010-01-21 Dixie Consumer Products Llc Paper cup manufacture with microencapsulated adhesive
CN101476265A (en) 2008-12-31 2009-07-08 鹅妈妈教育咨询（上海）有限公司 Zeolite corrugated cardboard, and manufacturing method and apparatus thereof
US20100181015A1 (en) 2009-01-22 2010-07-22 Kohler Herbert B Method for moisture and temperature control in corrugating operation
JP2010202996A (en) 2009-03-02 2010-09-16 Daio Paper Corp Converted paper
US20110019121A1 (en) 2009-07-24 2011-01-27 Au Optronics Corp. Flat panel display module
US20120015162A1 (en) 2010-06-22 2012-01-19 Societe D'enduction Et De Flockage Resin-coated material and process for manufacturing same
US20120048450A1 (en) 2010-09-01 2012-03-01 Lbp Manufacturing, Inc. Process of expediting activation of heat-expandable adhesives/coatings used in making packaging substrates
US20130160945A1 (en) 2010-09-10 2013-06-27 Henkel Corporation Adhesive having insulative properties
US20120100289A1 (en) 2010-09-29 2012-04-26 Basf Se Insulating compositions comprising expanded particles and methods for application and use
US20140131367A1 (en) 2012-11-14 2014-05-15 Pactiv LLC Multilayer article and method for making a multilayer article, blank, and insulating cup
JP6313163B2 (en) 2014-08-28 2018-04-18 Kddi株式会社 Message analysis apparatus, message analysis method, and computer program

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Bermesheva, E.V. "Zavisimost mezhdu vyazkouprugimi I adgezivnymi svoistvami polimernykh adgezivov. Dopolneni kriteriya liplosti Dalkkuista", 25 Sipozium Po Reologii, G.Ostashkov, Sep. 5-10, 2010, pp. 61, 62.
Popil, Roman E. et al. "Adhesive level effect on corrugated board strength-experiment and FE modeling." In: International progress in paper physics seminar. Oxford, Ohio: Miami University, 2006.
Popil, Roman E. et al. "Adhesive level effect on corrugated board strength—experiment and FE modeling." In: International progress in paper physics seminar. Oxford, Ohio: Miami University, 2006.

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11970634B2 (en) 2012-09-27 2024-04-30 Henkel Ag & Co. Kgaa Waterborne adhesives for reduced basis weight multilayer substrates and use thereof
US11773297B2 (en) 2017-07-18 2023-10-03 Henkel Ag & Co., Kgaa Dielectric heating of foamable compositions
US11926134B2 (en) 2017-08-25 2024-03-12 Henkel Ag & Co. Kgaa Process for forming improved protective eco-friendly pouch and packaging and products made therefrom
US11833788B2 (en) 2018-02-16 2023-12-05 Henkel Ag & Co, Kgaa Method for producing a multi-layer substrate

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